Matsumoto Yohei, Nakatake Daiki, Yazaki Ryo, Ohshima Takashi
Graduate School of Pharmaceutical Sciences, Kyushu University Maidashi Higashi-ku, Fukuoka, 812-8582, Japan.
Chemistry. 2018 Apr 20;24(23):6062-6066. doi: 10.1002/chem.201800957. Epub 2018 Mar 25.
A synthetic route to trans-configured tetrahydrothiophenes (THTs) through Fe(OTf) -promoted [3+2] cycloaddition of donor-acceptor cyclopropanes with thionoesters was developed. The cycloaddition proceeded in high yield with high diastereoselectivity, affording transient α-alkoxy THTs. Not only aromatic and aliphatic thionoesters, but also thionolactone were applicable to the present iron catalysis. Further transformation of the S,O-ketal functionality of the product was achieved in a highly trans diastereoselective manner. Moreover, the utility of our methodology was clearly demonstrated by the synthesis of enantioenriched trans-configured THTs.
通过Fe(OTf)促进供体-受体环丙烷与硫代酯的[3+2]环加成反应，开发了一种合成反式构型四氢噻吩（THTs）的路线。该环加成反应以高产率和高非对映选择性进行，生成瞬态α-烷氧基THTs。不仅芳香族和脂肪族硫代酯，而且硫代内酯也适用于目前的铁催化反应。产物的S,O-缩酮官能团以高度反式非对映选择性的方式实现了进一步转化。此外，对映体富集的反式构型THTs的合成清楚地证明了我们方法的实用性。
